Sodium Carbonate → 1-(tert-Butyl) 3-ethyl 4-(((trifluoromethyl)sulfonyl)oxy)-5,6-dihydropyridine-1,3(2H)-dicarboxylate

HRID 2428167Notes

Reaction equation

HRID 2428167 reaction equation
[CH2:1]([O:3][C:4]([CH:6]1[C:11](=[O:12])[CH2:10][CH2:9][N:8]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[CH2:7]1)=[O:5])[CH3:2].CCN(C(C)C)C(C)C.[O:29](S(C(F)(F)F)(=O)=O)[S:30]([C:33]([F:36])([F:35])[F:34])(=O)=[O:31].C([O-])([O-])=O.[Na+].[Na+]>C(Cl)Cl>[CH2:1]([O:3][C:4]([C:6]1[CH2:7][N:8]([C:13]([O:15][C:16]([CH3:18])([CH3:17])[CH3:19])=[O:14])[CH2:9][CH2:10][C:11]=1[O:12][S:30]([C:33]([F:36])([F:35])[F:34])(=[O:31])=[O:29])=[O:5])[CH3:2]

Participants

6

Reactant 4

HCID 10340Sodium CarbonateHCID 67749Trifluoromethanesulfonic anhydrideHCID 81531DiisopropylethylamineHCID 64208761-(1,1-Dimethylethyl) 3-ethyl 4-oxo-1,3-piperidinedicarboxylate

Product 1

HCID 222284091-(tert-Butyl) 3-ethyl 4-(((trifluoromethyl)sulfonyl)oxy)-5,6-dihydropyridine-1,3(2H)-dicarboxylateYield 95.7%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

4-Oxo-piperidine-1,3-dicarboxylic acid 1-tert-butyl ester 3-ethyl ester (30.9 g, 114 mmol) was dissolved in CH2Cl2 (800 mL). DIPEA (48.7 mL, 285 mmol) was added, and the reaction mixture was cooled to −78° C. A sol. of Tf2O (24.4 mL, 148 mmol) in CH2Cl2 (25 mL) was added slowly, while maintaining the temperature at −78° C. The mixture was stirred for 30 min at −78° C. The mixture was allowed to warm to rt, and aq. 10% Na2CO3 (400 mL) and ice were added. The layers were separated and the aq. layer was extracted with CH2Cl2 (2×). The combined org. layers were dried over MgSO4, filtered, and the solvents were removed under reduced pressure. Purification of the residue by FC (heptane→EtOAc/heptane 25:75) yielded the title compound (44.0 g, 91%). LC-MS: tR=1.05 min; ES+: 404.44.

Workup

  1. temperaturewhile maintaining the temperature at −78° C
  2. temperatureto warm to rt
  3. customThe layers were separated
  4. extractionthe aq. layer was extracted with CH2Cl2 (2×)
  5. dry with materiallayers were dried over MgSO4
  6. filtrationfiltered
  7. customthe solvents were removed under reduced pressure
  8. customPurification of the residue by FC (heptane→EtOAc/heptane 25:75)

Sources & evidence

ORD record
ord-433700698a5041cca43dc9d4027999e7
Source dataset
uspto-grants-2011_06
Patent number
US07968720B2

Reaction notes

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